Analysis of chromium and copper by cathodic stripping voltammetry with mixed ligands

Cathodic adsorptive stripping voltammetry is one of the most sensitive analytical methods for ultratrace analysis. The detection limit is usually lower than 10⁻⁹ mol/L. Most adsorptive stripping procedures have been focused on the one ligand/one analyte approach. In order to reduce analysis time and sample volume, the possibility of simultaneously determining several metals by cathodic stripping voltammetry using a mixture of ligands was explored, e.g., by Colombo and van den Berg (1997). Here, we describe a new procedure for quantifying chromium and copper using 2,2′-bipyridine and 8-hydroxyquinoline (oxine). The effect of various operational parameters such as buffer type, ligand concentration, potential and time collection were assessed and optimized. Possible interferences by trace metals and organic matter were also investigated. Applicability for fresh water is illustrated. Electronic Publication     

Mating system and individual reproductive success of sympatric anadromous and resident brook charr, <Emphasis Type="Italic">Salvelinus fontinalis</Emphasis>, under natural conditions

Salmonids are known for the occurrence in sympatry of two life-history forms, one that undergoes migration to sea before returning to freshwater to reproduce (anadromous) and one that inhabits freshwater without a migration phase (resident). Whereas one breeding population is often suggested by population genetic studies, mating patterns have rarely been directly assessed, especially when both sexes are found within each life-history form. By using highly polymorphic microsatellite loci and parentage analysis in a natural population of sympatric anadromous and resident brook charr (Salvelinus fontinalis), we found that gene flow occurred between the two forms and was mediated by resident males mating with both resident and anadromous females. Determinants of reproductive success, estimated by the number of surviving juveniles (ages 1 and 2 years), differed between the sexes. No strong evidence of the influence of size on individual reproductive success was found for males, whereas larger females (and hence most likely to be anadromous) were more successful. The higher individual reproductive success of anadromous fish compared to residents was mainly explained by this higher reproductive success of anadromous females. We suggest that resident males adopt a “sneaking” reproductive tactic as a way of increasing their reproductive success by mating with females of all sizes in all habitats. The persistence of the resident tactic among females may be linked to their advantage in accessing spatially constrained spawning areas in small tributary streams unavailable to larger females.     

Variation in sex steroids and phallus size in juvenile American alligators (Alligator mississippiensis) collected from 3 sites within the Kissimmee-Everglades drainage in Florida (USA)

This 3-year study was designed to examine variation in plasma sex steroids, phallus size, and the standard error (S.E.) associated with these endpoints in juvenile alligators collected from 3 sites within the Kissimmee-Everglades drainage (Florida, USA) with varying concentrations of sediment organochlorine contaminants. We hypothesized that decreased plasma sex steroid concentrations and phallus size would be observed in the higher contaminant site when compared to the intermediate and lower contaminant sites. Furthermore, we hypothesized that greater S.E. associated with these endpoints would be observed for the populations from more contaminated sites. We found that differences existed with females from the higher contaminant site exhibiting lower plasma estradiol-17beta (E2) and testosterone (T) concentrations. Males from the higher contaminant site exhibited smaller phallus sizes than males from the intermediate and lower contaminant sites. Smaller phallus size in this case differed from that reported in Lake Apopka male alligators [Gen. Comp. Endocrinol. 116 (1999) 356] in that a significant positive relationship between body size and phallus size existed. No difference among sites was observed in plasma T for males. Lower S.E. was associated with E2 and T concentrations in females from the higher contaminant site and in phallus size in males from the higher contaminant site. This pattern was opposite to what we had hypothesized. We concluded that variation in plasma E2 and T concentrations, phallus size, and the S.E. associated with these endpoints exists among the 3 sites with the patterns matching the patterns of organochlorine contamination, although S.E. patterns were opposite to what was predicted.     

Thyroid status in juvenile alligators (Alligator mississippiensis) from contaminated and reference sites on Lake Okeechobee,Florida, USA

Exposure to environmental contaminants has been shown to alter normal thyroid function in various wildlife species, including the American alligator (Alligator mississippiensis). Abnormalities in circulating levels of the thyroid hormone thyroxine (T₄) have been reported in juvenile alligators from several contaminated lakes in Florida. To further elucidate these functional thyroid abnormalities, this study examines the structure of thyroids and circulating T₄ concentrations from juvenile alligators collected from three sites of varying contamination on Lake Okeechobee, Florida. The following variables were used to characterize thyroid morphology: epithelial cell height, width and area, percent colloid, and follicle area. These variables were compared among study sites and between genders. No difference was detected in epithelial cell height, epithelial cell area, or follicle area among the sites, whereas significant differences in epithelial cell width (p=0.02) and percent colloid (p=0.008) were found. Animals from the most contaminated site (Belle Glade) had significantly greater epithelial cell widths and significantly less colloid present in their follicles compared to animals from the reference site (West). Gender did not have a significant interaction with site for any variable measured. Thyroxine (T₄) concentrations were elevated in the intermediately contaminated site (Conservation Area 3A) compared to the other sites (p<0.0001). It is proposed that the disruptions seen in Lake Okeechobee alligators are due to disruptions at both the thyroid and extra-thyroidal tissues.     

Comparison of metastable atom bombardment and electron capture negative ionization for the analysis of polychloroalkanes

A new method for quantifying C10-C13 polychloroalkanes (PCAs or chloroparaffins, CPs) in environmental samples using metastable atom bombardment ionization (MAB) and high resolution mass spectrometry is presented. Contrary to electron capture negative ionization (ECNI), MAB can produce spectra for molecules having a low number of chlorine atoms. These molecules are present in commercial PCAs and are responsible for a large fraction of the total PCA concentration in water samples analysed. Using ECNI or MAB, no molecular ion can be seen in the spectra. ECNI spectra contain important peaks corresponding to [M-Cl]- and [M-HCl]-* while the base peak in MAB spectra is [M-Cl]+ with no [M-HCl]+* present. The mass range for C10-C13 CPs is very large and scanning the masses for all the compounds involved would lead to a loss of sensitivity. Two chromatographic analysis are thus performed using high resolution selective ion monitoring with only a limited number of masses recorded per run. To reduce analysis time, a short capillary column is used. Application of this method to the analysis of high-volumes water samples (dissolved and particulates portions separately) from the St. Lawrence river near Quebec City using MAB is presented. Contribution of molecules with a low chlorine content in the samples account for between 10% and 46% to the total concentration. Congeners distribution between the different fractions indicates that molecules with a low number of carbon atoms are preferentially retained on the particulates. Within a carbon number group, there is a slight tendency to accumulate molecules with a high number of chlorine atoms in the dissolved fraction.     

Successful full‐scale enhanced anaerobic dechlorination at a NAPL strength 1,1,1‐TCA source area

Bioremediation of 1,1,1‐trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate‐reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full‐scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA‐ and pH‐related inhibition. © 2012 Wiley Periodicals, Inc.     

Size-dependent behavior of tuna in an array of fish aggregating devices (FADs)

Several lines of evidence indicate that aggregations of yellowfin tuna associated with floating objects are more frequently composed of small animals than larger ones. Also, the diet of small yellowfin tuna caught at anchored fish aggregating devices (FADs) around Oahu, Hawaii, was found to shift quite rapidly when these fish reached approximately 50 cm FL. In order to test for ontogenetic changes in aggregation behavior, we tagged and released two distinct size classes of yellowfin tuna in an array of anchored FADs around Oahu, Hawaii. Twenty-four yellowfin tuna 30–39 cm FL and 16 yellowfin tuna 63–83 cm FL were tagged with acoustic transmitters and released near anchored FADs equipped with automated acoustic receivers. Fish in the smaller size class stayed about 2.5 times longer at individual FADs than the larger fish (mean 4.05 days vs. 1.65 days) and displayed larger horizontal movements within the array. However, the durations of unassociated phases, residence times in the entire FAD array, percentage of time spent associated with FADs and numbers of movements between FADs did not show any difference between the two size groups. The observed size-dependent behavior is discussed in terms of physiological abilities, diet segregation and anti-predator behavior.     

The landscape epidemiology of foot-and-mouth disease in South Africa: A spatially explicit multi-agent simulation

This study aimed at understanding how landscape heterogeneity influences outbreaks of contagious diseases in southern Africa. Landscape attributes influence patterns of movement and behaviour of animal hosts, virus spread and survival, as well as land use practices. A multi-agent simulation was developed to represent the spatial and temporal dynamics of pathogens between human-livestock and wildlife interfaces at the fringe of large wildlife conservation areas. The model represents the three main elements associated with epidemics - populations, space, and time - to simulate direct contacts between wildlife and livestock. The dynamics of these populations emerge from interactions between agents and the landscape. The model was calibrated to represent the transmission of foot-and-mouth disease through direct contact at the border of the Kruger National Park in South Africa. In the region, African buffaloes (Syncerus caffer) act as reservoirs of the virus and spread the infection to domestic cattle bordering the park. We tested the sensitivity of various factors influencing contact rate between buffaloes and cattle, and thus the risk of foot-and-mouth disease transmission. Results show that cattle-buffalo contacts mostly depend on the range of displacements of cattle and buffaloes, as influenced by the landscape configuration, and on the number of fence breakages multiplied by the time between breakage and repair. Contacts take place not only close to water-points but also in grazing areas, within an area up to 6 km from the fence.     

Bioremediation of Dinitrotoluene in Aged Clay and Sandy Soils Using Pseudomonas Organisms,Spizizen Nutrient Medium and Prairie Silt Loam

This article describes the utility of Spizizen medium in effecting the release of 2,4 dinitrotoluene (DNT) from plasticized propellant in aged clay soil and of added Pseudomonas organisms in enhancing the rate of degradation of DNT in clay and sandy soils. DNT is an environmental problem because of its toxicity to mammals. It is proposed that the citrate in Spizizen medium chelates metals that form the aggregates of humin in aged clay soils, thereby releasing propellant components. Lack of awareness of DNT mobilization by citrate or other polyanions may lead to a potential underestimation of the 2,4 DNT present in aged contaminated soil and a potential increased release of DNT following exposure to solvents containing citrate or other polyanions. DNT in contaminated sandy soils was rapidly degraded when Pseudomonas and Spizizen medium were added (85% degraded in 20 days). Pseudomonas isolated/Torn soils at the Badger Plant have particular utility for the in situ degradation of 2,4 DNT in clay and sandy soils because they metabolize Spizizen medium, thrive in diverse climates, and have been selected for their ability to grow in soils contaminated with DNT. Mixture of either the contaminated clay soil or the contaminated sandy soil with uncontaminated prairie silt loam (20:80 ratio) facilitated management of the treatment process. This observation is important because of the widespread distribution, and hence low cost, of this soil type in the central United States.